Mercerizing compositions containing pinonic acid



United States Patent 2,974,002 MERCERIZING COMPOSITIONS CONTAINING PINONIC ACID Glen W. Hedrick, Lake City, F 1a., assignor to the United States of America as represented by the Secretary of Agriculture N0 Drawing. Filed June 30, 1959, Ser. No. 824,156

1 Claim. (Cl. 8-125) (Granted under Title 35, US. Code (1952), see. 266) V A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the mercerization of cotton. More particularly, this invention relates to novel mercerizing compositions containing pinonic acid.

Mercerization is a widely used process wherein cotton, in the form of yarn or fabric, is treated under tension with strong caustic soda solution and then, While still under tension, is washed until the cotton is free of caustic. The mercerization treatment, as usually practiced, so alters the cotton that it has greater smoothness, a permanent luster, improved dye afiinity and chemical reactivity, and increased tensile strength. If no tension is applied to the cotton during the treatment with the strong caustic, the cotton will shrink considerably and, upon washing, will show both greatly increased strength an dye afiinity, but no luster.

The majority of practical mercerizations are carried out using caustic concentrations between 22 and 25%, but caustic strengths ranging from about 14 to 28% may be used. In conjunction with the strong caustic solution, it is generally desirable to use a wetting agent or socalled mercerizing penetrant. The mercerizing penetrant dissolved in the caustic increases tremendously its pentrating power and helps to effect rapid and even wetting of the cotton with the caustic. Rapid, uniform, and etficient mercerization of the cotton is thereby made possible.

Most ordinary wetting agents cannot be used in the mercerizing process as they are not sufiiciently soluble in the strong caustic solutions. The conventional mercerizing penetrants are generally of two basic types, although numerous admixtures of types may be employed. One main group of penetrants is based on phenolic compounds, particularly cresylic acid (cresols), and the other group is based on noncresylichigh alcohols. The wetting power of the penetrant is usually increased by the addition of water-miscible organic solvents, frequently alocohols. The cresylic acid-type pentrants are more satisfactory for general use than the noncresylic type, but they have certain disadvantagesnamely, their odor is objectionable and they have irritating properties when in contact with the skin.

In general, mercerizing penetrants are employed at approximately 1% concentration, based on the volume of the mercerizing caustic solution. good penetrant required for the maximum effect rarely exceeds 2%. Some of the penetrants used in the prior art have high wetting powers, but usually only over a rather narrow range of caustic concentrations. Other penetrants can be used over a wider range of caustic concentrations, but they have poorer wetting powers.

It is an object of the present invention to provide novel mercerizing compositions containing pinonic acid. It is a further object of the invention to provide mercerizing The amount of a.

over a wide range of caustic concentrations and tempera- 2,974,002 Patented Mar. 7,1961

tures. Another object is to provide mercerizing compositions whose mercerizing penetrants do not possess objectionable or skin-irritating properties.

It has been discovered that pinonic acid, a carboxylic acid derivable from turpentine and represented by the following formula when mixed with butyl Cellosolve (i.e., Z-n-butoxyting properties with the cresylic acid-type mercerizing penetrants of the prior art.

The effectiveness of the pinonic acid mercerizing penetrant is quite surprising in view of the fact that other carboxylic acids having C C and C carbon chains are not generally satisfactory for use as wetting agents in mercerizing compositions. The unique structure and properties of pinonic acid are probably responsible for its effectiveness. Pinonic acid, as shown in the above formula, is a C monobasic acid containing a carbonyl (ketone) group. It is capable of forming, in strong caustic solutions, a sodium salt of both the carboxylic acid and the enol form of the ketone. It is believed that the enol form is important and that a certain amount of the enol salt is necessary for proper wetting; otherwise, the acid, because of the common ion effect, would not have the desired solubility for elfective wetting. Pinonic' acids" effectiveness is undoubtedly due to a relationship of molecular Weight, configuration, and solubility characteristics.

Pinonic acid suitable for use in the nrercerizing com,- positions of the present invention can be conveniently obtained from alpha-pinene, a major constituent of gum turpentine, by oxidation with ozone or potassium permanganate, as is well-known to those familiar with naval 7 stores products.

The mercerizing compositions of the present invention contain pinonic acid and butyl Cellosolve dissolved in caustic soda solutions of mercerizing strength, the pinonic acid being present in the mercerizing composition in from about 0.08 to 0.64 weight percent and the butyl Cellosolve being present in from about 0.72 to 0.16 weight percent, the lesser amounts of the butyl Cellosolve being employed with the greater amounts of the pinonic acid. It is generally preferred to mix the pinonic acid with the butyl Cellosolve, and then add the pentrant mixture to the caustic soda solution. The proportion of pinonic acid present in the pinonic acid-butyl Cellosolve penetrant mixture can be varied widely-from about 10 to wt. percent of the mixture. The preferred penetrant mixture contains 50 wt. percent of pinonic acid and 50 wt. percent of butyl Cellosolve. The quantity of penetrant mixture added to the caustic soda solution can be varied considerably, depending on the composition of idity of wetting desired by the operator. In general, about'l gram of penetrant mixture is preferred for each ml. of caustic soda solution, but efiective wetting of cotton can be achieved using as little as 0.25 or 0.5 g. of

3 the 50:50 mixture of pinonic acid and butyl Cellosolve for 100 ml. of caustic solution.

The concentration of the caustic soda solution used in the mercerizing compositions of the invention can be varied widely. It is generally preferred to employ a caustic concentration between about 255 and 315 g. of NaOH per liter of solution (i.e. about 21 to 25% NaOH). However, if the preferred penetrant mixture consisting of 50 wt. percent pinonic acid and 50 wt. percent butyl Cellosolve is employed, efiective wetting can be achieved using caustic concentrations ranging from about 165 to 345 g. of NaOH per liter (14 to about 28% NaOH).

The mercerizing compositions of the present invention maintain their effectiveness for wetting cotton over a rather wide range of operating temperatures. Using the preferred 50:50 mixture of pinonic acid and butyl Cellosolve as the penetrant in the mercerizing composition, almost instantaneous wetting of cotton with the mercerizing composition is achieved at temperatures ranging from 26 to 75 C.

The following examples are illustrative of certain details of the invention.

Example 1 Mixtures of pinonic acid and butyl Cellosolve, of the compositions indicated in the following table, were prepared. Each mixtures was tested for its elfectiveness 'a's a mercerizing penetrant (i.e., evaluated as a wetting agent for cotton yarn in caustic soda of mercerizing concentration) in accordance with tentative test method 43-1952, Evaluation of Penetrants for Mercerization, of the American Association of Textile Chemists and Colorists (1957 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, XXXIII, p. 156, Howes Publishing Co., Inc., New York, 1957). All tests were performed at a temperature of 26 C., using caustic concentrations of 285 grams of NaOH per liter of solution.

The data in the following table show the variations of Wetting times of the cotton yarn samples with the various pinonic acid-butyl Cellosolve mixtures.

Composition of Mercerizing Penetrant Wetting time Pinonic Butyl Celseconds acid, wt. losolve, wt.

percent percent '4 Example 2 Mixtures of pinonic acid and butyl Cellosolve, and of cresylic acids and butyl Cellosolve, of the compositions indicated in the following table, were prepared. Each mixture was tested for its effectiveness as a mercerizing penetrant according to the procedure of Example 1. A standard, commercial mercerizing penetrant (a mixture of polyhydric alcohols and cresylate) was also tested for comparison. All tests were performed at a temperature of 26 C., using caustic concentrations of 285 grams of. NaOH per liter of solution. The amount of penetrant used was varied as indicated in the following table.

The data in the table show the variations of wetting times of the cotton yarn samples with the mercerizing compositions containing the various kinds and concentrations of mercerizing penetrants.

Wetting time, seconds Mcrccrizing Penetrant Composition of Merg. or ml. penetrant for 100 N 0. cerizing Pcnetrant ml. caustic 1 Standard 1.1 1.0 3.0 18.2

Pinonic acid, 50 wt.

percent 2 Butyl Cellosolve, 50 l 3 wt. percent Pinonic acid, wt.

percent l 3 Butyl Cellosolve, 25 1 0 wt. percent Cresylictacids, 50 wt.

percen 4 Butyl Cellosolve, 50 1 3 wt. percent Cresylic acids, 75 wt.

percent 5 Butyl Cellosolve, 25 0 9 12 wt, percent 1 For mercerizing penetrants Nos. 2 and 3.

Example 3 A series of tests for effectiveness as mercerizing penctrants was conducted on the five mercerizing penetrant compositions of Example 2. In this series, one gram or milliliter of penetrant was used for milliliters of caustic solution, and the caustic strength was varied from to 465 grams of NaOH per liter of caustic solution. The other conditions of the tests were as previously described.

The data in the following table shown the relative efiectiveness of the various penetrants in the merceriz- 55 ing compositions over the wide range of caustic concentrations.

Wetting time, seconds Mercerizing Composition of Mercerizing Pelistl'filll Penetrant Caustic concentration, gms.NaOH per liter 1 Standard 8.5 1.7 1.5 2.5

Pinonic aicd, 50 wt. percent. 2 Butyltcellosolve,50wt.per- 2.2 0.7 0.9 1.5 1.7 2.7

cen Ptnonic acid, 75 wt. percent. 3 ButylzCellosolve,25wt.per- 1.9 1.1 1.4 2.7

cen Cresylic acids, 50 wt. percent 4 ButylgCellosolveJOwhper- 1.6 0.8 1.1 1.4 1.0 2.3 8

cen Cresylic acids, 75 wt. percent 5 ButylCel1osolve,25wt.per- 0.7 0.9 1.0 1.6 1.9 0

cent.

Example 4 A series of tests for effectiveness as mercerizing penetrants was conducted on the five mercerizing penetrant compositions of Example 2. In this series, one gram of milliliter of penetrant was used for 100 milliliters of caustic solution. The caustic concentration was 285 grams of NaOI-I per liter of caustic solution. The tests were conducted at temperatures of 26, 50 and 75 C. The other conditions of the tests were as previously described.

The data in the following table show the relative effectivenes of the five penetrants in the mercerizing compositions at the various temperatures.

Wetting time, seconds hgeircer- 2 ng Pel etrant Composition of Mercerizing Penetrant Temperature, O.

1 Standard 1. 7 3. 7 2 {Plnomc acid, 50 wt. percent 1 5 1 0 1 o Butyl Cellosolve, 50 wt. percent 3 {Piuonic acid, 75 wt. percent 1 1 2 6 9 2 Butyl Cellosolve, wt. percent... 4 {Cresylic acids, wt. percent l 4 1 a 1 4 Butyl Cellosolve, 50 Wt. percent {Cresylic acids. wt. percent... 0 7 0 7 Butyl Cellosolve. 25 wt percent I claim:

caustic soda solution of mercerizing strength, from about 0.08 to 0.64 weight percent of pinonic acid, and from about 0.72 to 0.16 weight percent of butyl Cellosolve, the

lesser amounts of butyl Cellosolve being employed with the greater amounts of pinonic acid.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Summers et aL: American Dyestuff Reporter, vol. 47, pp. 571-573, August 25, 1958.

6 humus.

A mercerizing composition comprising an aqueous I 

